CN112390940A - Catalyst for polyester synthesis - Google Patents
Catalyst for polyester synthesis Download PDFInfo
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- CN112390940A CN112390940A CN202011267871.1A CN202011267871A CN112390940A CN 112390940 A CN112390940 A CN 112390940A CN 202011267871 A CN202011267871 A CN 202011267871A CN 112390940 A CN112390940 A CN 112390940A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract
The invention relates to a catalyst for polyester synthesis, which is prepared by the following steps: (1) adding the substance A (amino acid or amino acid ester), titanate, silicate and metal acetate into a mixed solution of dihydric alcohol (1, 4-butanediol) and monohydric alcohol (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol) for reaction; (2) removing small molecules generated by the reaction; (3) and adding a phosphoric acid compound into the system after the micromolecules are removed, and reacting again to obtain the catalyst for synthesizing the polyester. The catalyst for polyester can be used for preparing high molecular weight and low chroma polyester materials, has high activity and low dosage, does not need to be compounded or compounded with other catalysts in the process of synthesizing polyester, and can obtain high-quality products only by single use.
Description
Technical Field
The invention belongs to the technical field of catalysts for polyester synthesis, and relates to a catalyst for polyester synthesis.
Background
Polyesters synthesized from diacids and diols generally include esterification processes and polycondensation processes. In the esterification process, raw material monomers are esterified and dehydrated under the action of a catalyst to generate oligomers, and then small molecules are removed through further polycondensation reaction under the high vacuum condition, so that the molecular weight is increased. The selection of the catalyst is particularly important in the reaction process, which not only affects the selection of the reaction rate and the reaction conditions, but also affects the quality of the product, such as molecular weight, color and the like, thereby indirectly affecting the performance and the application range of the product.
At present, in the synthesis process of polyester, the adopted catalyst is mainly a compound of two elements of titanium and antimony. In addition, germanium catalysts are also used in some applications. Antimony catalysts such as antimony trioxide, antimony acetate, antimony butanediol, antimony glycol and the like have the advantages of low cost, less side reaction in the reaction process, lower activity, easy pollution of contained heavy metals to the environment and easy gray appearance of the obtained product; the germanium catalyst is mainly germanium oxide, germanate and the like, has low activity, high price and less resources, and is not beneficial to industrialization; the titanium catalyst has high activity and belongs to an environment-friendly series compound without heavy metal, and is the focus of research in polyester synthesis catalysts in recent years.
The titanium catalyst undergoes a certain development process in the polyester synthesis. From the early use of inorganic salts of titanium (such as potassium titanium oxalate) and titanates (such as tetrabutyl titanate and tetraisopropyl titanate) to the combined use of titanium catalysts used today with other metal promoters, the problems of poor product stability, poor color and low molecular weight exist. And because the titanium catalyst is easy to hydrolyze in water to generate white precipitate, the activity of the catalyst is reduced, the dosage is increased, the production cost is increased, and the product performance is also influenced.
Patent CN 104693428B provides a preparation method of high molecular weight poly (butylene succinate), which adopts a titanium silicalite molecular sieve as a catalyst, and utilizes the characteristic of large specific surface area of the titanium silicalite molecular sieve to obviously improve the molecular weight of a polyester product;
patent CN 100528929C discloses a process for preparing aliphatic polyester, which adopts a composite catalyst system of metal alkoxide and titanium silicon oxide to compound with phosphoric acid compounds, so as to synthesize aliphatic dibasic acid glycol ester with high molecular weight and good chroma.
Patent CN 103130992A relates to a method for preparing high molecular weight poly (butylene adipate-terephthalate), wherein the catalyst is a mixture of metal oxide and organic titanium ester, and the method of adding the catalyst in the esterification stage and adding the heat stabilizer in the polycondensation stage is adopted to improve the molecular weight of the polymer and reduce the terminal carboxyl value of the polymer.
However, the common titanium catalysts of the above types are not only added in a large amount in the reaction process, but also have the problem that the titanate catalyst is easy to hydrolyze, so the catalyst is of little significance to industrial production.
With the intensive research of a large number of researchers on titanium catalysts, the current industrial production is mostly a composite catalyst compounded by the titanium catalysts and phosphoric acid compounds, the catalyst solves the problem that the common titanium catalysts are not resistant to hydrolysis, and polyester products with better quality are obtained:
patent CN 101671435B provides a compound catalyst with hydroxycarboxylic acid and phosphoric acid compounds as complexing agents, and titanium alkoxide, silicon alkoxide and dihydric alcohol as main components, and is used for synthesis of PBS polyester to obtain a product with a low B value. But when the catalyst is used, the reaction temperature is higher, and the energy consumption of production is increased.
Patent CN 104629033B discloses a method for producing low acetaldehyde titanium polyester, which comprises reacting dihydric alcohol with titanate to generate cyclic titanium alkoxide, and then reacting with hydroxycarboxylic acid, metal acetate and phosphoric acid to generate a compound liquid catalyst, thereby solving the problems of slow polymerization rate and high acetaldehyde residual amount of PET polyester prepared by the prior titanium catalyst. However, the PET polyester obtained by the polymerization of the catalyst has low intrinsic viscosity, and the application range of the product is narrowed.
Patent CN 105061744B provides a good-color PBS polyester product with a number average molecular weight of more than 10 ten thousand and a tensile strength of more than 36MPa, which is prepared by adding titanate compound catalyst after butanediol, an organic phosphorus compound and a hindered phenol antioxidant react. However, the thermal stabilizer needs to be added in the polycondensation stage, and the operation steps are complicated.
Patent CN 101182370A invents a catalyst composed of a liquid composed of phosphorous acid compounds, a titanium compound and a magnesium compound, which can be used for synthesizing PET, PTT and PBT polyesters, and the catalyst has stable property and easy storage, but the catalyst has complex manufacturing process, the color L value of the synthesized polyester is low, the viscosity is low, and the industrial production significance is small.
Patent CN 104558574B synthesizes a titanium polyester catalyst, metal salt compounds, titanates and dihydric alcohol are mixed and reacted, then phosphoric acid compounds are added for continuous reaction to prepare the catalyst, and the problems that in the prior art, the prepared dihydric alcohol compound catalyst of titanium has high activity to cause side reactions such as thermal degradation and the like, but titanium dioxide/ethylene glycol slurry is required to be supplemented in the operation process, the process steps are complicated, and the reaction temperature is too high are solved.
Therefore, it is very important to research a novel catalyst for polyester synthesis.
Disclosure of Invention
The present invention has been made to solve the above problems occurring in the prior art, and an object of the present invention is to provide a catalyst for polyester synthesis. The invention utilizes amino acid or amino acid ester, titanate, silicate ester and metal acetate to complex with environment-friendly phosphoric acid compounds, not only solves the problem that the common titanium catalyst is easy to hydrolyze, but also can greatly inhibit the generation of byproducts in the reaction process, and can synthesize biodegradable polyester products with excellent performance at lower temperature.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding the substance A, titanate, silicate ester and metal acetate (cocatalyst) into a mixed solution of 1, 4-butanediol (as a solvent) and monohydric alcohol (as a diluent and a cosolvent) for reaction; the substance A is amino acid or amino acid ester; the monohydric alcohol is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol; preferably ethanol;
(2) removing small molecules generated in the step (1);
(3) and adding a phosphoric acid compound serving as a complexing agent into the system from which the small molecules generated by the reaction are removed to carry out a secondary reaction to prepare the catalyst for synthesizing the polyester.
As a preferred technical scheme:
the catalyst for polyester synthesis has the advantages that the reaction temperature in the step (1) is 50-140 ℃, and the reaction time is 2-10 h; the reaction temperature of the step (3) is 50-140 ℃, and the reaction time is 2-10 h.
According to the catalyst for polyester synthesis, the micromolecules generated in the step (2) by removing the reaction are subjected to reduced pressure distillation, and the generated high-boiling-point micromolecule product is carried out by using low-boiling-point monohydric alcohol, wherein the absolute pressure of the reduced pressure distillation is 1-5 kPa.
The catalyst for synthesizing polyester has the mass ratio of the substance A to the titanate of 0.2-1: 1, preferably 0.4-0.8: 1; the mass ratio of the silicate ester to the titanate is 0.05-0.1: 1, preferably 0.05-0.08: 1; the mass ratio of the metal acetate to the titanate is 0.001-0.002: 1, preferably 0.0015-0.002: 1; the mass ratio of the phosphoric acid compound to the titanate is 0.5-1.5: 1, preferably 0.9-1.5: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1-2: 1, preferably 1.5-1.9: 1; the mass ratio of the monohydric alcohol to the metal acetate is 20-70: 1, preferably 30-50: 1.
In the above-mentioned catalyst for polyester synthesis, the amino acid or the amino acid ester is serine methyl ester, threonine methyl ester, glycine methyl ester, alanine methyl ester, phenylalanine methyl ester, valine methyl ester, leucine methyl ester, isoleucine methyl ester, glycine, alanine, phenylalanine, threonine, valine, leucine or isoleucine, preferably serine methyl ester.
The catalyst for polyester synthesis as described above, wherein the titanate is one or more of diethyl titanate, tetra-t-butyl titanate, tetrabutyl titanate and tetraisopropyl titanate.
In the above-mentioned catalyst for synthesizing a polyester, the silicate is at least one of methyl orthosilicate and ethyl orthosilicate.
In the above catalyst for polyester synthesis, the metal acetate is one or more of aluminum acetate, cobalt acetate, zinc acetate, magnesium acetate and calcium acetate.
The catalyst for polyester synthesis is characterized in that the phosphoric acid compound is triethyl phosphonoacetate, trimethyl phosphonoacetate, diethyl methylphosphonoacetate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate or polyphosphoric acid, and is preferably green, nontoxic and environment-friendly triethyl phosphonoacetate.
The catalyst for synthesizing the polyester is a light yellow viscous transparent liquid; wherein the content of titanium element is 3.39-7.97 wt%.
The catalyst for synthesizing the polyester can be used for preparing high molecular weight low-chroma polyester materials, is superior to the prior art, can be completely added in the pulping process, and simplifies the industrial operation steps.
The preparation of the catalyst for polyester adopts a complexing technology, titanate and amino acid or amino acid ester are subjected to exchange reaction, and the exchanged product and a phosphoric acid compound form Ti-O-P coordination bond for compounding; the added silicate plays a role in concerted catalysis in the synthesis of the polyester. Compared with other similar catalysts, the catalyst prepared by the invention has the following advantages:
(a) the catalytic activity is high, the dosage is small, and the production cost is reduced;
(b) because titanate and amino acid or amino acid ester form the complex structure with phosphorus atom after the exchange reaction, have overcome the instability of titanate, make the polyester synthesis of the invention use catalyst not react with air and water, and does not produce the white and precipitate, has avoided the loss of catalyst in the reaction process, convenient long-term storage;
(c) the addition of the metal acetate not only plays a role of a cocatalyst, but also causes the system to be alkalescent due to the dissociation of the metal acetate in the system, thereby greatly inhibiting the side reaction of the tetrahydrofuran generated by the cyclization of the 1, 4-butanediol serving as the raw material in the polyester synthesis process and improving the product quality;
(d) the polyester can be synthesized without being compounded or compounded with other catalysts, and a high-quality product can be obtained by using the catalyst alone.
In polyester synthesis, common metal catalysts (such as metal simple substances, metal acetates, metal oxides and the like) are generally applied, but the metal catalysts (such as metal simple substances, metal acetates, metal oxides and the like) catalyze polyester to have slow reaction rate and poor product performance, so that the metal catalysts are gradually replaced by titanate catalysts. The catalytic mechanism of the metal catalyst (such as metal simple substance, metal acetate, metal oxide, etc.) mainly includes a complex coordination mechanism and a central coordination mechanism.
(1) The complex coordination mechanism, the specific reaction mechanism, is as follows:
the hydroxyethyl in the polyester molecular chain can easily generate an inner ring-shaped compound by itself, the inner ring is formed by hydrogen bond combination of hydrogen on hydroxyl in the hydroxyethyl and oxygen on carbonyl, and hydrogen atoms are replaced by metal in a metal catalyst in the process of molecular chain growth; the metal in the complex provides an empty orbit to coordinate with lone-pair electrons of the carbonyl group, so that the electropositivity of carbonyl carbon is increased, and the carbonyl oxygen on the other hydroxyethyl group attacks the carbonyl carbon in the complex and is combined with the carbonyl carbon, so that the polycondensation reaction is completed, and a cyclic complex is formed; then the cyclic complex reacts with a catalyst to generate an epoxy compound, and carbonyl oxygen on an ester group and metal ions generate a coordinate bond, so that an active structure is formed, the hydroxyl is favorable for attacking carbonyl carbon atoms, and the reaction process is accelerated.
(2) The center coordination mechanism, the specific reaction mechanism, is as follows:
the catalyst reacts with two hydroxyethyl groups in the catalysis process, and coordinates with carbonyl oxygen of the hydroxyethyl groups to form a complex; the complex is further coordinated with a polyester esterified molecular chain to obtain a new complex; the new complex reacts again to give a polycondensation product.
In the above reaction mechanism, either the complex coordination mechanism or the central coordination mechanism, the metal atom is required to replace the hydrogen atom in the internal ring structure formed by the hydroxyethyl group, so that the subsequent chain extension step can be continued. However, the activation energy required by the replacement process is high, the replacement process is slow, so that the catalytic efficiency of the metal catalyst is greatly limited, the polycondensation reaction rate of the polyester is slow, and the performance of the product is also influenced.
Compared with metal catalysts, the titanate catalyst has a better catalytic effect, but the common titanate catalyst is easy to hydrolyze due to the inherent instability of ester bonds, so that the application of the titanate catalyst is limited. The titanium complex catalyst prepared by the invention overcomes the problem that the common titanium complex catalyst is easy to hydrolyze due to different complex mechanisms, and has lower catalytic reaction activation energy and greatly improved catalytic efficiency.
In the preparation process of the catalyst for polyester synthesis, silicate ester is added to play a role in concerted catalysis, so that the reaction rate of polyester synthesis is greatly increased, but the catalyst is mainly used for catalyzing Ti. The main compounding mechanism of the catalyst prepared by the invention is as follows: the titanate and the amino acid or the amino acid ester are subjected to exchange reaction to form a Ti-N bond with larger bond energy and more stability, so that the instability of the Ti-O bond caused by small bond energy is overcome, and the catalyst has the hydrolysis resistance; the product after the exchange reaction and the phosphoric acid compound can form Ti-O-P coordination bond for compounding. In the polymerization reaction process, although the phosphoric acid compound can play a role of a heat stabilizer, the phosphoric acid compound and a catalyst need to be added in batches during the reaction, which increases inconvenience for actual production. Because the titanium atoms directly form a complex structure with carbonyl in the catalysis process of the catalyst for polyester synthesis, the activation energy required in the process is low, and the reaction rate is high, the catalyst has high catalytic activity, the time required by polyester synthesis is reduced, the reaction time of polyester products at high temperature is reduced, the occurrence of thermal degradation side reaction is reduced, and the chromaticity and the molecular weight of the polyester products are greatly improved.
The main catalytic mechanism of the catalyst is as follows: firstly, titanium catalyst CAT is complexed with polyester intermediate A to generate CAT.A, and then CAT.A and A form unstable intermediate complex CAT.A2Then the unstable intermediate complex is decomposed into stable CAT & P and releases alcohol micromolecules, and finally the CAT & P reacts with A to transfer catalytic active points to a new intermediate A, so that a new catalyst body is formed and the catalysis is continued, and meanwhile, the polyester molecular chain is increased.
Has the advantages that:
(1) the catalyst for polyester is simple in preparation method, environment-friendly and safe;
(2) the catalyst for polyester has high activity and low consumption, and can be used alone to obtain high-quality products without being compounded or compounded with other catalysts in the polyester synthesis process.
Drawings
FIGS. 1 to 3 are schematic diagrams of the complexing mechanism of a metal catalyst;
FIGS. 4 to 6 are schematic diagrams of the mechanism of center coordination of a metal catalyst;
FIGS. 7 to 8 are schematic diagrams of the main compounding mechanism of the catalyst for polyester synthesis according to the present invention;
FIGS. 9 to 12 are schematic diagrams showing the main catalytic mechanism of the catalyst for polyester synthesis according to the present invention;
wherein R is1Is composed of
(n is a positive integer and n is not less than 2), R2Is composed of
R3Is composed of
NH2R4The amino acid methyl ester or the amino acid represented,
in particular to
R’5Is composed of
R”5Is composed of
OR”’5Is composed of
OCH3、
M is metal atom such as Ca, Zn, Mg, Mn, Co, etc., and X represents acetate ion CH3COO-Or an oxygen atom.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Fig. 1 to 3 are schematic diagrams of a complex coordination mechanism of a metal catalyst in the prior art, fig. 4 to 6 are schematic diagrams of a central coordination mechanism of a metal catalyst in the prior art, fig. 7 to 8 are schematic diagrams of a main compounding mechanism of a catalyst for polyester synthesis of the present invention, and fig. 9 to 12 are schematic diagrams of a main catalysis mechanism of a catalyst for polyester synthesis of the present invention (addition of silicate ester plays a role in a concerted catalysis, greatly increasing a reaction rate of polyester synthesis, but mainly uses Ti as a catalyst).
Example 1
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid ester (serine methyl ester), titanate (diethyl titanate), silicate (methyl orthosilicate) and metal acetate (aluminum acetate) into 1, 4-butanediol and monohydric alcohol (ethanol) for reaction; the reaction temperature is 50 ℃, and the reaction time is 8 hours; the mass ratio of the amino acid ester to the titanate is 0.4: 1; the mass ratio of silicate ester to titanate is 0.06: 1; the mass ratio of the metal acetate to the titanate is 0.001: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.2: 1; the mass ratio of the monohydric alcohol to the metal acetate is 35: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 1 kPa;
(3) adding a phosphoric acid compound (triethyl phosphate) into the system with the small molecules removed for secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 80 ℃, and the reaction time is 3 hours; the mass ratio of the phosphoric acid compound to the titanate is 0.8: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 7.62 wt%.
The catalyst for synthesizing the polyester is used for synthesizing the PBT polyester, the dosage of the catalyst (calculated by the mass of titanium element) is 50ppm of the total mass of the raw materials for synthesizing the polyester, and the intrinsic viscosity of the prepared PBT polyester is 1.14 dL-g-1The chroma L value is 92, and the b value is 3.9; the tensile strength was 52 MPa.
Comparative example 1
Tetrabutyl titanate is used as a catalyst, and triethyl phosphate is used as a heat stabilizer to synthesize the PBT polyester. The catalyst amount was the same as in example 1, and the intrinsic viscosity of the PBT polyester obtained was 0.74dL g-1(ii) a The color L value is 79, and the b value is 10; the tensile strength was 40 MPa. Comparing example 1 with comparative example 1, it can be found that, when the PBT polyester is synthesized by using tetrabutyl titanate which is a common catalyst for synthesizing polyester in the prior art, the synthesized PBT polyester has lower intrinsic viscosity, poorer chroma and lower tensile property. This is because the common titanate catalyst is easy to hydrolyze, resulting in low catalytic efficiency, increased degree of side reaction during the reaction, and poor product performance.
Example 2
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid ester (threonine methyl ester), titanate (diethyl titanate), silicate (methyl orthosilicate) and metal acetate (cobalt acetate) into 1, 4-butanediol and monohydric alcohol (ethanol) for reaction; the reaction temperature is 60 ℃, and the reaction time is 9 hours; the mass ratio of the amino acid ester to the titanate is 0.3: 1; the mass ratio of silicate ester to titanate is 0.08: 1; the mass ratio of the metal acetate to the titanate is 0.0013: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.2: 1; the mass ratio of the monohydric alcohol to the metal acetate is 50: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 1 kPa;
(3) adding a phosphoric acid compound (triethyl phosphonoacetate) into the system after the micromolecules are removed for carrying out a secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 80 ℃, and the reaction time is 3 hours; the mass ratio of the phosphoric acid compound to the titanate is 0.8: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 7.84 wt%.
Example 3
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid ester (glycine methyl ester), titanate (diethyl titanate), silicate (methyl orthosilicate) and metal acetate (zinc acetate) into 1, 4-butanediol and monohydric alcohol (n-propanol) for reaction; the reaction temperature is 60 ℃, and the reaction time is 8 hours; the mass ratio of the amino acid ester to the titanate is 0.2: 1; the mass ratio of the silicate ester to the titanate is 0.05: 1; the mass ratio of the metal acetate to the titanate is 0.0015: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.5: 1; the mass ratio of the monohydric alcohol to the metal acetate is 50: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 1.2 kPa;
(3) adding a phosphoric acid compound (triethyl phosphonoacetate) into the system after the micromolecules are removed for carrying out a secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 70 ℃, and the reaction time is 4.5 h; the mass ratio of the phosphoric acid compound to the titanate is 0.6: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 7.97 wt%.
Example 4
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid ester (alanine methyl ester), titanate (tetra-tert-butyl titanate), silicate (methyl orthosilicate) and metal acetate (magnesium acetate) into 1, 4-butanediol and monohydric alcohol (n-propanol) for reaction; the reaction temperature is 70 ℃, and the reaction time is 7 hours; the mass ratio of the amino acid ester to the titanate is 0.5: 1; the mass ratio of silicate ester to titanate is 0.08: 1; the mass ratio of the metal acetate to the titanate is 0.0018: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.1: 1; the mass ratio of the monohydric alcohol to the metal acetate is 40: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 1.2 kPa;
(3) adding a phosphoric acid compound (triethyl phosphonoacetate) into the system after the micromolecules are removed for carrying out a secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 60 ℃, and the reaction time is 6 hours; the mass ratio of the phosphoric acid compound to the titanate is 0.5: 1.
The obtained catalyst for synthesizing the polyester is a light yellow viscous transparent liquid, wherein the content of titanium element is 6.68 wt%.
Example 5
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid ester (phenylalanine methyl ester), titanate (tetra-tert-butyl titanate), silicate (methyl orthosilicate) and metal acetate (calcium acetate) into 1, 4-butanediol and monohydric alcohol (ethanol) for reaction; the reaction temperature is 70 ℃, and the reaction time is 6.5 h; the mass ratio of the amino acid ester to the titanate is 0.55: 1; the mass ratio of silicate ester to titanate is 0.07: 1; the mass ratio of the metal acetate to the titanate is 0.00121; the mass ratio of the 1, 4-butanediol to the titanate is 1: 1; the mass ratio of the monohydric alcohol to the metal acetate is 60: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 1.5 kPa;
(3) adding a phosphoric acid compound (triethyl phosphonoacetate) into the system after the micromolecules are removed for carrying out a secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 90 ℃, and the reaction time is 2 hours; the mass ratio of the phosphoric acid compound to the titanate is 0.85: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 5.7 wt%.
Example 6
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid ester (valine methyl ester), titanate (tetra-tert-butyl titanate), silicate (methyl orthosilicate) and metal acetate (a mixture of aluminum acetate and zinc acetate in a mass ratio of 1: 1) into 1, 4-butanediol and monohydric alcohol (methanol) for reaction; the reaction temperature is 70 ℃, and the reaction time is 6 hours; the mass ratio of the amino acid ester to the titanate is 0.35: 1; the mass ratio of the silicate ester to the titanate is 0.09: 1; the mass ratio of the metal acetate to the titanate is 0.0019: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.4: 1; the mass ratio of the monohydric alcohol to the metal acetate is 65: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 1.5 kPa;
(3) adding a phosphoric acid compound (trimethyl phosphonoacetate) into the system after the micromolecules are removed for carrying out a secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 50 ℃, and the reaction time is 8 hours; the mass ratio of the phosphoric acid compound to the titanate is 0.9: 1.
The obtained catalyst for synthesizing the polyester is a light yellow viscous transparent liquid, wherein the content of titanium element is 5.14 wt%.
Example 7
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid ester (leucine methyl ester), titanate (tetrabutyl titanate), silicate (ethyl orthosilicate) and metal acetate (a mixture of magnesium acetate and calcium acetate in a mass ratio of 1: 1) into 1, 4-butanediol and monohydric alcohol (isobutanol) for reaction; the reaction temperature is 85 ℃, and the reaction time is 6 hours; the mass ratio of the amino acid ester to the titanate is 0.7: 1; the mass ratio of the silicate to the titanate is 0.055: 1; the mass ratio of the metal acetate to the titanate is 0.002: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.7: 1; the mass ratio of the monohydric alcohol to the metal acetate is 25: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 2 kPa;
(3) adding a phosphoric acid compound (trimethyl phosphonoacetate) into the system after the micromolecules are removed for carrying out a secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 60 ℃, and the reaction time is 7 hours; the mass ratio of the phosphoric acid compound to the titanate is 1.2: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 3.86 wt%.
Example 8
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid ester (isoleucine methyl ester), titanate (tetraisopropyl titanate), silicate (ethyl orthosilicate) and metal acetate (cobalt acetate) into 1, 4-butanediol and monohydric alcohol (isobutanol) to react; the reaction temperature is 90 ℃, and the reaction time is 6 h; the mass ratio of the amino acid ester to the titanate is 0.6: 1; the mass ratio of the silicate ester to the titanate is 0.1: 1; the mass ratio of the metal acetate to the titanate is 0.0011: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.3: 1; the mass ratio of the monohydric alcohol to the metal acetate is 40: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 3 kPa;
(3) adding a phosphoric acid compound (diethyl methylphosphonoacetate) into the system after the micromolecules are removed for carrying out a secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 100 ℃, and the reaction time is 2 hours; the mass ratio of the phosphoric acid compound to the titanate is 1.3: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 5.12 wt%.
Example 9
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid (glycine), titanate (a mixture of tetrabutyl titanate and tetraisopropyl titanate with the mass ratio of 1: 1), silicate (ethyl orthosilicate) and metal acetate (zinc acetate) into 1, 4-butanediol and monohydric alcohol (methanol) for reaction; the reaction temperature is 90 ℃, and the reaction time is 5 hours; the mass ratio of the amino acid to the titanate is 0.8: 1; the mass ratio of the silicate to the titanate is 0.075: 1; the mass ratio of the metal acetate to the titanate is 0.0017: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.8: 1; the mass ratio of the monohydric alcohol to the metal acetate is 55: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 4 kPa;
(3) adding a phosphoric acid compound (diethyl methylphosphonoacetate) into the system after the micromolecules are removed for carrying out a secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 80 ℃, and the reaction time is 3 hours; the mass ratio of the phosphoric acid compound to the titanate is 1.5: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 3.71 wt%.
Example 10
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid (alanine), titanate (a mixture of tetrabutyl titanate and tetrabutyl titanate with the mass ratio of 1: 2), silicate (ethyl orthosilicate) and metal acetate (zinc acetate) into 1, 4-butanediol and monohydric alcohol (n-butanol) for reaction; the reaction temperature is 95 ℃, and the reaction time is 5.5 h; the mass ratio of the amino acid to the titanate is 0.9: 1; the mass ratio of silicate ester to titanate is 0.088: 1; the mass ratio of the metal acetate to the titanate is 0.002: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.4: 1; the mass ratio of the monohydric alcohol to the metal acetate is 50: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 2 kPa;
(3) adding a phosphoric acid compound (trimethyl phosphate) into the system with the small molecules removed for secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 75 ℃, and the reaction time is 6 hours; the mass ratio of the phosphoric acid compound to the titanate is 1.4: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 3.72 wt%.
The catalyst for synthesizing the polyester is used for synthesizing the PET polyester, the dosage of the catalyst (calculated by the mass of titanium atoms) is 100ppm of the total mass of the raw materials for synthesizing the polyester, and the intrinsic viscosity of the prepared PET polyester is 1.24 dL-g-1The chroma L value is 90, and the b value is 4; the tensile strength was 53 MPa.
Comparative example 2
Tetrabutyl titanate is used as a catalyst, trimethyl phosphate is used as a heat stabilizer and is used for synthesizing the PET polyester, the dosage of the catalyst is the same as that of the example 10, and the intrinsic viscosity of the prepared PET polyester is 0.83 dL-g-1(ii) a The chroma L value is 80, and the b value is 8.5; the tensile strength was 40 MPa. Example 10 and comparative example 2 were carried outThe comparison shows that the PET polyester synthesized by adopting the tetrabutyl titanate which is a common catalyst for synthesizing the polyester in the prior art has lower intrinsic viscosity, poorer chroma and lower tensile property. This is because the common titanate catalyst is easy to hydrolyze, resulting in low catalytic efficiency, increased degree of side reaction during the reaction, and poor product performance.
Example 11
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid (phenylalanine), titanate (tetrabutyl titanate), silicate (ethyl orthosilicate) and metal acetate (zinc acetate) into 1, 4-butanediol and monohydric alcohol (n-butanol) for reaction; the reaction temperature is 105 ℃, and the reaction time is 4 hours; the mass ratio of the amino acid to the titanate is 0.74: 1; the mass ratio of the silicate ester to the titanate is 0.065: 1; the mass ratio of the metal acetate to the titanate is 0.0016: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.9: 1; the mass ratio of the monohydric alcohol to the metal acetate is 70: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 2 kPa;
(3) adding a phosphoric acid compound (triethyl phosphate) into the system with the small molecules removed for secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 65 ℃, and the reaction time is 10 hours; the mass ratio of the phosphoric acid compound to the titanate is 1.45: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 3.39 wt%.
Example 12
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid (threonine), titanate (tetrabutyl titanate), silicate (a mixture of methyl orthosilicate and ethyl orthosilicate in a mass ratio of 1: 1) and metal acetate (aluminum acetate) into 1, 4-butanediol and monohydric alcohol (tert-butanol) for reaction; the reaction temperature is 110 ℃, and the reaction time is 4 hours; the mass ratio of the amino acid to the titanate is 0.86: 1; the mass ratio of silicate ester to titanate is 0.058: 1; the mass ratio of the metal acetate to the titanate is 0.0016: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.6: 1; the mass ratio of the monohydric alcohol to the metal acetate is 60: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 2 kPa;
(3) adding a phosphoric acid compound (triethyl phosphate) into the system with the small molecules removed for secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 90 ℃, and the reaction time is 7 h; the mass ratio of the phosphoric acid compound to the titanate is 0.95: 1.
The obtained catalyst for synthesizing the polyester is a light yellow viscous transparent liquid, wherein the content of titanium element is 4.07 wt%.
Example 13
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid (valine), titanate (tetrabutyl titanate), silicate (a mixture of methyl orthosilicate and ethyl orthosilicate in a mass ratio of 1: 2) and metal acetate (aluminum acetate) into 1, 4-butanediol and monohydric alcohol (isopropanol) to react; the reaction temperature is 125 ℃, and the reaction time is 4 hours; the mass ratio of the amino acid to the titanate is 0.45: 1; the mass ratio of silicate ester to titanate is 0.08: 1; the mass ratio of the metal acetate to the titanate is 0.001: 1; the mass ratio of the 1, 4-butanediol to the titanate is 2: 1; the mass ratio of the monohydric alcohol to the metal acetate is 45: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 5 kPa;
(3) adding a phosphoric acid compound (triethyl phosphate) into the system with the small molecules removed for secondary reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 120 ℃, and the reaction time is 9 hours; the mass ratio of the phosphoric acid compound to the titanate is 1.1: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 3.89 wt%.
Example 14
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid (leucine), titanate (tetraisopropyl titanate), silicate (a mixture of methyl orthosilicate and ethyl orthosilicate in a mass ratio of 2: 1) and metal acetate (aluminum acetate) into 1, 4-butanediol and monohydric alcohol (isopropanol) to react; the reaction temperature is 130 ℃, and the reaction time is 3 hours; the mass ratio of the amino acid to the titanate is 1: 1; the mass ratio of the silicate ester to the titanate is 0.09: 1; the mass ratio of the metal acetate to the titanate is 0.0015: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.5: 1; the mass ratio of the monohydric alcohol to the metal acetate is 35: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 5 kPa;
(3) adding a phosphoric acid compound (triphenyl phosphate) into the system with the small molecules removed for re-reaction to prepare the catalyst for synthesizing the polyester; the reaction temperature is 135 ℃, and the reaction time is 8 hours; the mass ratio of the phosphoric acid compound to the titanate is 1: 1.
The obtained catalyst for synthesizing the polyester is a light yellow viscous transparent liquid, wherein the content of titanium element is 4.71 wt%.
Example 15
The catalyst for synthesizing the polyester is prepared by adopting the following steps:
(1) adding amino acid (isoleucine), titanate (tetraisopropyl titanate), silicate (ethyl orthosilicate) and metal acetate (aluminum acetate) into 1, 4-butanediol and monohydric alcohol (isopropanol) to react; the reaction temperature is 140 ℃, and the reaction time is 2 hours; the mass ratio of the amino acid to the titanate is 0.25: 1; the mass ratio of silicate ester to titanate is 0.095: 1; the mass ratio of the metal acetate to the titanate is 0.002: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1.3: 1; the mass ratio of the monohydric alcohol to the metal acetate is 70: 1;
(2) removing small molecules generated by the reaction by adopting a reduced pressure distillation mode, wherein the absolute pressure of the reduced pressure distillation is 5 kPa;
(3) adding a phosphoric acid compound (polyphosphoric acid) into the system from which the small molecules are removed to react again to prepare the catalyst for synthesizing the polyester; the reaction temperature is 110 ℃, and the reaction time is 6 hours; the mass ratio of the phosphoric acid compound to the titanate is 1.28: 1.
The obtained catalyst for synthesizing the polyester is light yellow viscous transparent liquid, wherein the content of titanium element is 5.77 wt%.
Claims (10)
1. The catalyst for synthesizing polyester is characterized by being prepared by the following method:
(1) adding the substance A, titanate, silicate ester and metal acetate into the mixed solution of 1, 4-butanediol and monohydric alcohol for reaction; the substance A is amino acid or amino acid ester, and the monohydric alcohol is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol;
(2) removing small molecules generated by the reaction;
(3) and adding a phosphoric acid compound into the system after removing the micromolecules generated by the reaction to react to prepare the catalyst for synthesizing the polyester.
2. The catalyst for synthesizing polyester according to claim 1, wherein the reaction temperature in the step (1) is 50-140 ℃, and the reaction time is 2-10 h; the reaction temperature of the step (3) is 50-140 ℃, and the reaction time is 2-10 h.
3. The catalyst for polyester synthesis according to claim 1, wherein the small molecules produced by the reaction in step (2) are removed by distillation under reduced pressure; the absolute pressure of the reduced pressure distillation is 1-5 kPa.
4. The catalyst for synthesizing polyester according to claim 1, wherein the mass ratio of the substance A to the titanate is 0.2-1: 1; the mass ratio of the silicate ester to the titanate is 0.05-0.1: 1; the mass ratio of the metal acetate to the titanate is 0.001-0.002: 1; the mass ratio of the phosphoric acid compound to the titanate is 0.5-1.5: 1; the mass ratio of the 1, 4-butanediol to the titanate is 1-2: 1; the mass ratio of the monohydric alcohol to the metal acetate is 20-70: 1.
5. The catalyst for polyester synthesis according to claim 1, wherein the amino acid or the amino acid ester is serine methyl ester, threonine methyl ester, glycine methyl ester, alanine methyl ester, phenylalanine methyl ester, valine methyl ester, isoleucine methyl ester, glycine, alanine, phenylalanine, threonine, valine, leucine or isoleucine.
6. The catalyst for polyester synthesis according to claim 1, wherein the titanate is one or more of diethyl titanate, tetra-t-butyl titanate, tetrabutyl titanate and tetraisopropyl titanate.
7. The catalyst for polyester synthesis according to claim 1, wherein the silicate is at least one of methyl orthosilicate and ethyl orthosilicate.
8. The catalyst for polyester synthesis according to claim 1, wherein the metal acetate is one or more of aluminum acetate, cobalt acetate, zinc acetate, magnesium acetate and calcium acetate.
9. The catalyst as claimed in claim 1, wherein the phosphoric acid compound is triethyl phosphonoacetate, trimethyl phosphonoacetate, diethyl methylphosphonoacetate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, or polyphosphoric acid.
10. The catalyst for polyester synthesis according to claim 1, wherein the content of titanium element in the catalyst for polyester synthesis is 3.39-7.97 wt%.
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| CN113801312A (en) * | 2021-09-01 | 2021-12-17 | 万华化学集团股份有限公司 | Composite catalyst containing organic semiconductor and application thereof |
| CN114621426A (en) * | 2022-04-11 | 2022-06-14 | 山东瑞丰高分子材料股份有限公司 | Catalyst for synthesizing degradable polyester and preparation method and application thereof |
| CN116574247A (en) * | 2023-06-30 | 2023-08-11 | 浙江大学 | Preparation method of butanediol polyester |
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